学科进展系列报告
题 目:Organocopper Compounds:From Elusive to Isolable Species
报告人:Prof. Gerard van Koten
Utrecht University The Netherlands
主持人:麻生明 教授
时 间:10月13日(星期五)上午10:00
地 点:遗传楼407会议室
欢迎全体研究生和职工参加
Organocopper Compounds: From Elusive to Isolable Species
Gerard van Koten
Organic Chemistry and Catalysis,
Debye Institute for Nanomaterials Science,
Faculty of Science, Utrecht University,
3584 CG Utrecht, The Netherlands
g.vankoten@uu.nl
The first reports on copper-mediated organic reactions and speculations about the role of presumed organocopper compounds as intermediates or transient species date back to the 19th Century. Since that time, copper salt-mediated and, much later, copper catalyzed C-X bond forming reactions (X = C, O or N) have been developed. Phenyl- and methylcopper(I) (highly explosive as a dry solid) were the first organocopper materials synthesized by Reich (1923) and Gilman (1952), respectively. However, it was not until the late 1960’s and early 1970’s that the first pure organocopper(I) compounds, that are also stable at room temperature, were isolated and structurally characterized. Recently, by the application of clever design and new synthetic approaches, even organocopper(II) and (III) compounds have been isolated, species that during the greater part of last century were considered elusive. Significantly, these species had for some time been surmised, via kinetic and computational studies, to play a key role in copper mediated and catalyzed C-X bond forming reactions.
In this personal account (Organometallics, 2012, 31, 7634-7646) the various stages along which organocopper chemistry developed, with a steadily pace, will be highlighted. Special attention will be paid to a discussion of the structural features of polynuclear organocopper(I) compounds in the solid state and in solution. The tailored construction of copper aggregates (including cuprate type species) with mixed anionic (organo, halide, thiolate, carboxylate, cyanide, etc) groupings, making use of the supramolecular behavior of the aggregates, will be discussed.